Process for producing hydrazine



Jan. 29, 1957 J, RoBELL Paocass FOR PRoDUcING HYDRAZINE 2 sheets-sheet 1 Filed Oct. 29, 1952 Ammonu\ Flat Spray Nozzle Fig. 5.

INVENTOR John Robell ATTORNEY Jan. 29, 1957 J. Roar-:LL 2,779,661

PROCESS FOR PRODUCING HYDRAZINE Filed Oct. 2.9, 1952 2 Sheets-Sheet 2 O2, Air or O2+Air` Fuel Gas NH3 Non Condensoble Gos k Air, r Oxygmed Air Combustion or xygen und W Reaction Preheaters Chamber Ncnugcl l(gusI Coolers NH3 G05 Gondensers NH;5

Voporizer NH H CH N Liquid N owcZo' 2 4 2 2 N2H4+H2O +ANH3+CO2 y etc. Gos

NH3+N.C. Gas +002 C0 N2H4+H2 f 2 +r-|H5+co2 ou* V H2O NH3 a C02 Hydruzlnef C02 Sfrl er Gus Scrubber Separcfion Steam pp Uni* V H o l 2 N.G. Gos

v 2:36 Liquid Liquid N2H4 Gus Hydrazine Sii-Concentration N2H4+H2o :10

unir 5 V CO2 Compressors Hydrozine N. C. Gus Product to Fuel 5 INVENTOR John Robell N.C. lNan Condensuble BY @MJ IVW@ ATTORNEYl United States Patent O 2,779,661 PROCESS FOR PRGDUCING HYDRAZINE John Robell, West Hempstead, N. Y., assignor to Guggenheim Brothers (1949), a copartnership Application October 29, 1952, Serial No. 317,533 4 Claims. (Cl. 231-190) This invention relates to chemistry and has for an object the provision of an improved process for producing chemical compounds. More particularly, the invention contemplates the provision of a process for subjecting various chemical compounds to the action of various reagents at elevated temperatures to produce, in the gaseous state, valuable products of decomposition and transformation and comprising in different arrangements and proportions atoms contained in the original chemical compounds.

The terms reaction, decomposition and transformation are used herein as substantial equivalents in order to cover the elds of direct chemical reaction, decomposition and polymerization or re-combination, among others. In some of its more specic aspects the invention is concerned with the conversion of saturated or stable compounds to unsaturated and relatively unstable or more highly reactive compounds.

The invention provides a process of the type in which bodies or streams of fluid reagents are brought into reacting relationship under conditions such as to promote desired reactions, decompositions or transformations with the production of bodies of gases containing products of the reactions, decompositions or transformations, and, thereafter, the gaseous products of the reactions, decompositions or transformations are subjected to conditions `that promote or insure the preservation and recovery of the desired products. Thus, for example, the invention provides a process in which a chemical compound or radical or other component of a high-temperature body of gas requiring for its production a temperature higher than its maximum temperature of stability, or its decomposition temperature, and at which it necessarily exists in the gaseous state is cooled rapidly to a temperature below its maximum temperature of stability, or below its decomposition temperature.

The iluid reagents are brought into contact in a hightemperature reaction zone, and the gaseous reaction product flows to a relatively low-temperature cooling and stabilizing zone. The rates of flow of the i'luid reagents and the iluid reaction products, the temperature of the reaction zone, and the temperature of the cooling and stabilizing zone are so regulated that suicient time is allowed to provide the energy and develop the temperature required to produce a suitable rate and degree of reaction between the reagents and a suitable yield of the desired reaction product, and cooling of the desired reaction product to a temperature below its maximum temperature of stability, or below its decomposition temperature, is effected before an undesirable degree of decomposition of a desired reaction product can take place.

The energy required for producing temperatures and effecting reactions may be provided in any suitable manner, as, for example, by means of hot gases produced in any suitable manner and utilized directly or subjected to superheating prior to use, by means of open llames, by means of electric arcs established and maintained in contact with the reagents, by means of electric resistance elements disposed in the high-temperature reaction zones in contact with the reagents, by means of hot solid surfaces heated electrically or by'combustion means, or by means of any two or more of such sources of energy.`

rce

to gas), or by changes of direction, or, I may utilize a.A

combination of such factors.

The speed of removal of the desired reaction product and its associated gaseous reaction products will be determined by the rate and state of introduction of the:

reagents into the high-temperature reaction .zone coupled, necessarily, with the effectiveness of means provided for permitting the llow of the gaseous reaction products from the high-temperature reaction zone to the lowtempera ture cooling and stabilization zone.

The speed employed for the ow of fluid reagents into the high-temperature reaction zone or the speed em ployed for the flow of gaseous reaction products from the immediate zone of reaction, or both, will be deter mined by the characteristics of the reaction products, particularly with respect to their rates of production and their actual or potential rates and times or periods of decomposition. When the rate of production of a desirable reaction product is high, the rate oi introduction of reagents into the reaction zone and the rate of removal of reaction products from the reaction zone to the cooling and stabilizing zone should be high. If, on the other hand, the rate of production of a desirable reaction product is low, the rate of introduction of thereagents into the reaction zone may be low and the rate of removal of the reaction products may be relatively low. In the latter case, the predetermined rates of introduction and removal will depend, largely, upon the characteristics of the reaction products with respect to their lives or actual or potential rates and times or periods of decomposition at their temperature of production. When the rate of production exceeds the rate of decomposition at the ternperature of production, the rate of removal may be reduced within the limits of economic factors. Of course, it is to be understood that the rates of introduction and removal referred to herein are relative, as the term rate implies, and they are not to be carelessly confused with speeds of flow, for, obviously, a quantity of fluid material introduced into a high-temperature reaction zone at a relatively low temperature may have its volume multiplied so that its rate of discharge through an outlet of the same cross-sectional area as the inlet may have its speed of llow multiplied in some proportion..

Dissipation of the sensible heat of the gaseous reaction product to provide for cooling and. stabilization may be provided for in any suitable manner. Thus, for example, a fluid-cooled heat exchanger or other chilling means may be so disposed with respect to the zone of reaction as to permit either immediate orl suitably delayed contact with the gaseous reaction products. Such a fluid-cooled heat exchanger should be so designed with respect to contact surfaces and cooling fluid ilow as to permit effective absorption of the sensible heat of the gases, whether the gases are maintained at a fixed pressure or the gases are subjected to sudden expansion. Preferably, such a heat exchanger should be provided and associated with means permitting the use of a liquid having a high heat of vaporization at a temperature be-v heat absorption capacity resulting from the heat of vaporization.

Ina'suitablefcases,l one oi-more ofthe reagents-may be introduced in excess into or immediately adjacent to the reaction Zone at a temperature lower than the temperature ofreaetion to provide-for .orpromote :effective cooling and.stabilizationsofthe desired reaction product. Such- Oneor-.morle-1feagents-canbe employedeffeetivelyfin the y liquid .state tto, permit the utilization for cooling yand sta`- biliz'ationv purposes j of the cooling'.- effect resulting l from thel .absorption .of heat 'required forv its vaporization :or-` expansioritlk Similarly,y a chemicallynon-reactiveliquid substance'having a high 'heat of vaporizaton snch,-for exampleyaswvatercan be .introduced into' the Ireaction 1 zonento permit. utilizationfort coolingV and. stabilization purposes .ofthe coolingk effect' resulting from. -the-fabsorp-V tionof heat required for its vaporization.

VTheinvention.provides an effective proeesstfor converting;or ytransforming stable or unsaturated compounds .such as-hydrocarbons andammonia into relatively unstable or unsaturated; compounds.

Among the preferred processesiof my. .invention -is Athat involving .the:use .ofan open combustion ameas a source ofl energy for producing temperatures and effectingyreactions and transformations. The llame may function solely tofprovideheat foi-.promoting oneorimore desired chemical reactions or' transformations in the high-temperature reaction or transformation zone through itsinluence onk a single compoundor through its influence on two. or more. compounds or agents, or, thenatures of the-combustible materials? and thev oxidizing Vmaterialremployed in Apro-` ducing the. frame may be such as to result in providing heatforpromoting the one or more desired .chemical reactions or transformations and, also, in providing one or more chemicalagents or reagents that prornotetor,y enter into the desired chemical reactions or transformations. In a process employing an opcncombustion flame, one or mo-re of the same 4or additional compounds or. reagents that may be required for producinga `desired endproduct are contacted with the flame in the. form of l use, asia source of energy for developing temperatures.

and'eecting reactions andtransformationa'of a hotl gase. ous product formed in a suitable 'chamberiinzany suitable manner and issuing from an outlet port or orifice ofthe chamber in the form of a blast-or tongue. of controlled shape and.-crosssectional area. The hot 'gaseous `product employed preferably is a product resulting from the .combustion (oxidation) of natural gas withL air in anenclosedy combustion chamber or in a multiplicity of enclosed come bustion chamberseach-provided with anoutlet port Yor. orifice which, advantageously, may be in the form :of-an elongated. slot topermit the issuance of a flatblast,.that` is, a blast having a relatively long cross-sectional axis 'and a relatively short cross-sectional axis normal :to .theflong axis.V Oxygen or oxygen-enrichedair may be'employedin `burning the natural gas. The blast ofi-hot gas-v may function solely for promoting one or more desired chemical reactions or transformations in the high-temperature reaction or transformation zone through its influence on a v. single compound ory through its influence on twov or l more compoundsor reagents, or the. combustible material andthe oxidizing material employed in producingthe, hot gaseous product .may be such as to result in providing, heatl for promoting the one for more. desired'. chemical'v reactionsy or transformations and,4 also, in: proyidingffone or 4more chemical agentsor reagentsvthatrprOmOIegor,enten into the 2desired chemical reactions .or .transformat ions., kIna procesdslvtemployingya ,hotf blast." of '..cornbustion 'gas,. onegtvornnorey-of the` Lsame-or'jadditionalcompounds .or f reagents that may, beurequiredffor .,producing a desired end product are contacted with the hot gaseous blastintheform ofV a high-speed or high-velocity stream o1", body,

coniayfzircon, mullite,fberillia thoria, titaniaf-or mixturesL of such refractory materials. Basic silicatesof knownl' types also may be employed.

The high-speed stream of gas comprising acornpound .y to be modified orl transformed maybe employed'fasa'-' heat-dissipating; or cooling agent, either aloneor icorn junction vvith other heat dissip'atingor` cooling means, Atof rcducethe temperature of the gaseous reaction product and effect stabilization or prevent decomposition yofthe desired product. The speed or velocity oftheYV body jor stream of gas and its point or manner ofcontact with Athe hot blast should be such as toprovide4 effectively for,v utilizing the heatl energy of -the blastlwhile, at the same', time, providing for suiciently rapid cooling of theA desireI 'i reaction or ltransformation productto effect its stabiliza-fv-r tion or prevent its decomposition. The speed or velocity of thestream of gas used for quenching mayfbei'n either the subsonic range or the-supersonic rangen' Prefejra'lzvl'y,A

the speed or velocity of the-streamofgasused for quenching or forv quenching and reaction Vor transformation should be inl excess offive Ahundred feetv per'second. In

approaching the Asonic range, shock waves may be encoun-vfr tered or developed,` so I prefer tooperatev'lith a nozzle* properly designed `producing a shock vvfree stream at the,v reaction zone sovas to providefor smooth -r'eaction'andvr the production of uniform results@ The-'gas employed for;v heat dissipation or cooling may be preheated ytoa temperature below thedecomposition temperature ofA the one or more compounds or reagents contained therein,` ifdesired, in order more effectively/to promotel reaction or transformation in that portion ofthe stream orfbody thatcontacts the hot blast-at thedesirablefreaction or transformation temperature.-

The high-speed stream or-'body-offheatfdissipating or cooling gas'maybe contacted with the-hotgas blast Yiny any suitable manner. practicing Vthe invention, the stream Vofheat-dissipat'ing gas is formed as a flat spray havingfin cross-sectionpshor'tj and long axes, and it is directed intoco'n'tact with the hotf gas blast in such manner that its long-.axisfintersects'the longitudinal `axis ofthe gas blast. IIighly`etfective`con-v tact maybe achieved whenthe-lor'igaxis of the sprayanfd the median plane of the spray form right angles withv the longitudinal axis of thefhot gas blast-and-Wheri contact is made` immediately adjacent ftotheuoutl'e't port combustion chamber.

A flat blast .preferably is employed, but a blast having any desired configuration Ymay be employcdfinl practicing i' the invention. The long axis of thespraylmay, advan`V tageously, be greater in length than the vWidth of; the

blast.l

According .to anotherV preferred method of. practicing the invention, the blast of hot gas and the-stream of heati dissipating gas are' employed in aco-axialfrelationshipf A blast of hot gas 'having any desired cross-sectionalcon-` guration .is formed, and.l thestream of -lieatdissip'ating gas is formed as an envelope surrounding the blastf'vvitha According toa preferred method of ,ofI the f fcreased when the blast of hot arrasar ,The surface of the flame or blast-.of hot gas or other heated .element or sourcejof heat energy'should .be of such length or quality or have such'characteristics.that the `time of .contact of thecompound to be modiedtwith the source of heat-energy should be. shorter'than one Vone- `hundredth of a second and, in the case of compounds like hydrazine, `should be one ten-thousandth to a millionth .of a second or shorter.

"Whenthe compound to bemodiedor transformed is used in' developing the combustion gas blast, `an additional quantity of the `compound at a relatively low temperature p. may be introduced into the blast fof hotgas resulting from combustion in .order to effect coolingandfurther reaction,

; modification or. transformation.

"fin the `preferred. form .of my invention, I employ a i blast. of hot: combustion,gasproduced by oxidation of Amethane with oxygen, air or oxygenfenriched air. `The resulting gaseous product, When `quenched with ammonia or with. a saturated'` hydrocarbon compound will yield products .comprisingunsaturated hydrogen-nitrogen compounds or unsaturated hydrocarbon compounds.

The .invention is `ofparticular importance With respect to hydrazine productionwhich `can be .effected through transformationof ammonia. "Therefore, it Willbe dej scribed hereinafter with respect to hydrazine production inthe` utilization .of principles and :factors hereinbefore pointed out and discussed.

`The present invention,`in soffar` as it relates to the production of hydrazine, is based on.my discovery that -substantial amounts of hydrazine .areproduced when a combustible gas is burned with air, pure oxygen or oxygen- 4enriched `air and the fresultinghot gaseous combustion product is cooled or .chilled by means of a high-velocity stream or body of ammonia.

- bymeans of a high-Velocity stream of ammonia. Among the combustible gases employed are hydrogen, acetylene,

ammonia; methane, fethane, propane,l butane.A and carbon monoxide. These gasescaneither bepremixed with oxy- `gen before allowing them to burnor fed separatelyto a Y suitable diusion type burner.

i prefer to use methane as thecombustible`gas and to employ natural gas forcombustion because of its methane content.

I have found that the yield of hydrazine increases as *the linear Velocityof ammoniaused for cooling or chilling the hot blast of gaseous combustion 'product is.increased and that,within certain limits, this yield isin- Ldependent of the volumetric ratioof ammoniato oxygen used. Hov/evenenough ammonia preferably jshould .be `used to cool the hot gaseous combustion product to a temperaturelow enough so'that the hydrazine formed is stable and will not decompose thermally. Ammonia in `amount insulicient to produce the desiredcooling eifect otained, however, lwith gaseous ammonia. A further increase in fthe `yield isobtainedif both the ammonia and vthe gasestused for producing theblast of hot gaseous lcombustion product are preheated. The ammonia should not be `preheated `to such extent that thetemperature of the resulting body of gaseous `reaction products exceeds the decomposition temperature of hydrazine.

I have found, also, that the yields of hydrazine are ingaseous combustion p roducts is contactedwith the stream or body of ammonia at the `shortest possible distance from the outlet port ofthe #combustion chamber.

In carrying 'out a process oftheinvention involving the burning of .methane withf-air in asuitablecombustion t chamber, or pre-combustion chamber, .to :produce a blast of hot, gaseous.` combustion; products, Lmay employ methane and air in any ,suitablefIatiosg In` employing 5 pure methane', I may employ air in greateror lesser proportions than 'thatv which provides the .approximately ftheoretical ratio. ofV 9.5 volumes of air to 1.0 volume of Vmethane requiredffor complete combustion. When natural gas is employed for its methane content, the ratio of aiuto-naturalggas employed should be varied `to provide the air and natural gas in amounts corresponding to the theoreticalratio, or in amounts such that air is employed in an` amount greater or lesser than `the amount corresponding to that theoretically -required for complete combustion .of the.y particular natural gas product employed.

Three possible mechanisms couldfexplain `the .formation of hydrazine inthe process:

1. Thermal` decomposition .of ammonia according to the following reactions:

t :NH3=NH2 -i-H NHzel-NHz:Naf-I4 H-|-H=H2 2.12. Action of-fradicals on-1 ammonia accordingto the following mechanism:

NHs-i-radicals from flame :NH2-,'-H2O t (or H2) NHz-l-NHaNzI-Li v 3. Hydrazine lmay `bevformed by `direct oxidation of rammoniawithtoxygen `from air `according to:

Accordingto"thishypothesismethane may burn with air and thus`= provide fthe heat to 4bring the reactants to a 'temperature at which theVV above reaction will p'roceedat a reasonably high rate. The oxygen for the above re- `a`ctio`n may be Vsupplied by a very small part of the air 40 introduced with the methane.

4 In a preferred method of operation for the production of,.hydrazinc,.9.5 to 10.5 volumes of air are'tnixed with 1 volumev of methane and themixtureis ignited in a re- `fractory lined. pre-combustion chamber provided with an outlet orifice of such dimensions and shape that a hat blast or tongue of hot gas issues therefrom.. A flat stream of gaseous ammonia emerging from a suitable nozzle is directed at right angles to the longitudinal axis of the gas blast or tongue. Contact of the ammonia with the hot blast or tongueof gas results in the production'of hydra- Zine which followed immediately by chilling and cooling the resulting body of gas containing the hydrazine. The stream of reacting and quenching or cooling ammonia should be directed against the blast or tongue of hot gas at a point, along a line `or in a plane as close as is reasonably possible to the` outlet orice ofthe pre-combustion chamber Vin order that substantially the total heat energy contained in the blast may be conserved to permit its utilization substantially at the temperature of production of the gas.

In carrying out pilot plant operations involving the ignition and burning of a mixture of methane and air under different conditions `of operation with respect to such factors Vas quantities and ratios of airt and methane, preheating of the reagents to different temperature, and contacting of the `hot gaseous blast with quenching or cooling ammonia, I have obtained reaction products which, upon cooling and condensing, formed aqueous condensates containing from 0.77 percent `to 1.85 percent of hydrazine by weight. l

The following data illustrate conditions maintained and results obtained in carrying out a` process, which may be considered a typical process of the invention, `in which methane was burned with air in `a pre-combustion chamber provided with/a rectangular outlet .of restricted I mixed air and combustible gas (not shown).

cross-sectional area to produce a flat blast or tongue of hot gas which issued from the outlet and against which a fiat stream of ammonia of a width substantially the same as the width of the blast was directed from a nozzle disposed 1.5 millimeters from the outlet orice and 1.0 millimeter from the plane of the blast or tongue of gas with its median plane forming right angles with the median plane and the longitudinal axis of the gas blast:

Quantity of methane fed to the burner- 4.35 S. C. F. I-I.

Quantity of air fed to the burner 45.6 S. C. F. H. Ratio of methane to air 1 to 10.5 Ammonia quenching stream 192.5 S. C. F. H. Temperature of reaction products 415 F.

The invention will be better understood from a con sideration of the following description in conjunction with the accompanying drawings in which Fig. 1 is a perspective of a combustion chamber or burner provided with a rectangular outlet port and having an interior of rectangular cross-section but of greater cross-sectional area than the cross-sectional area of the outlet port, a portion of the wall of the chamber being broken away to show the interior;

Fig. 2 is a perspective of a combustion chamber similar to that shown in Fig. 1 but differing therefrom in that the outlet port and the interior of the chamber are of similar cross-sectional areas;

Fig. 3 is a section taken substantially along the line 3 3 of Fig. l;

Fig. 4 is a section taken substantially along the line 4--4 of Fig. 3; and

Fig. 5 is a flowsheet illustrating a process for producing hydrazine in accordance with the invention.

The combustion chamber or burner shown in Figs. 1, 3 and 4 of the drawing comprises an outer metal casing and a metal plenum chamber 11 to which the outer casing 10 is attached. The interior of the casing is provided with a high-temperature insulating refractory lining 12 having corrugated walls, so shaped as to provide a rectangular outlet port or blast opening 13 and a recf tangular interior combustion chamber 14 of greater crosssectional area than the cross-sectional area of the outlet port or blast openirny 13, and a ceramic plate 15 provided with ports 16 communicating with the interior of the plenum chamber lill and the interior of the combustion chamber. The total area of the ports 16 preferably is smaller than the cross-sectional area of the blast opening or outlet port 13. A single pipe connection 17 communicating with the interior of the plenum chamber is formed integrally with the plenum chamber. All parts of the combustion cham-ber or burner are iuterlocked by their shapes and the sequence of assembly.

In the operation of the combustion chamber or burner, the pipe connection 17 is connected to a source of pre- The mixture of gasand air entering the interior yof the combustion chamber through the ports 16 burns within the combustion chamber or burner. Combustion proceeds along and in contact with the surface of the high-temperature insulating refractory lining 12. The corrugated walis of the lining attain white hot incandescencc, and intense radiation plays, from wall to wall across the path of travel of the gases during the course of their interreaction thus accelerating `the rate of combination of the com bustible gas and the oxygen of the air. A super-heated 8 blast or tongue of gas 18 (Figs. 3 and 4), undiluted by secondary air, issues from the outlet port or blast opening 13.

As indicated by Figs. 3 and 4, operation of the combustion chamber or burner shown in Fig. 1 produces a flat blast of gas 18 having a relatively short vertical axis and a relatively long horizontal axis. In employing such a blast of hot gas to produce hydrazine, an ammonia spray device 19 provided with a at spray nozzle 21 is so disposed as to deliver into contact with the blast of hot gas a iiat spray 22 having in cross-section long and short axes with the long axis greater in length than the width of the blast of hot gas, the flat spray of ammonia being directed into contact with the blast of hot gas in such manner as to project beyond the side edges of the blast of hot gas with its long axis intersecting the longitudinal axis of the blast of hot gas adjacent to the plane of issuance of the blast of hot gas from the outlet port or blast opening 13 and with its long axis and its median plane forming right angles with the longitudinal axis of the blast of hot gas.

The combustion chamber or burner shown in Fig. 2 is similar to that shown in Fig. 1, comprising an outer metal casing 23 and a metal plenum chamber 24 to which the casing 23 is attached. The interior of the casingl is provided with a high-temperature insulating lining 25 having corrugated walls, so shaped as to provide a rectangular outlet port or blast opening 26 and a rectangular interior combustion chamber 27 having a cross-sectional area substantially the same as the cross-sectional area of the outlet port or blast opening 26, and a ceramic plate 28 provided with ports 30 communicating with the interior of the plenum chamber 24 and the interior of the combustion chamber. As in the case of the burner or combustion chamber shown in Fig. 1, the total area of the ports 30 preferably is smaller than the cross-sectional area of the blast opening or outlet port. A single pipe connection 31 communicating with the interior of the plenum chamber is formed integrally with the bronze casting forming the plenum chamber.

In the operation of the combustion chamber of burner shown in Fig. 2, the pipe connection 31 is connected to a source of pre-mixed air and combustible gas (not shown). The burner shown in Fig. 2 functions, in operation, to develop conditions and produce results substantially identical with the conditions developed and results produced in the operation of the burner or combustion chamber shown in Fig. l.

The specific procedure outlined in Fig. 5 will be clear from a consideration of the legends applied thereto and the flow chart forming a part thereof. The ow sheet of Fig. 5 shows la process for producing hydrazine in which preheated combustible gas and pre-heated air are reacted in a suitable combustion chamber in the presence of ammonia in the gaseous state, and the gaseous reaction product is first contacted with a primary cooler employing water as an internal cooling agent (as in a tubular exchanger) and, thereafter, is contacted with a secondary cooler employing liquid ammonia as an internal cooling agent (as in a tubular heat exchanger). A liquid product containing hydrazine and a gaseous product containing hydrazine are produced, and the two products are treated appropriately to effect the recovery of hydrazine. Provision is made for the separation and recovery of unaltered ammonia associated with the hydrazine and for the utilization of hydrogen and nitrogen associated with the hydrazine for the regeneration of ammonia for re-use in the process.

In the process of the invention involving the use of a blast of hot gas in the production of hydrazine, I prefer to operate under conditions such as to permit utilization of the blast of hot gas at a temperature as close as possible to its temperature of production. In some instances, desirably high temperatures can be developed by employing combustible mixtures consisting of substantially pure oxygen or oxygen enriched air and a substantially pure combustible gas in stoichiometric proportions. Preheating of the components of combustible mixtures which also contain diluent materials such, for example, as nitrogen, when air or oxygen-enriched air is used as the source ot oxygen, can be utilized for developing temperatures higher than those directly attainable when the components are ignited at normal atmospheric temperatures. Similarly, pre-heating may be employed to aid in developing higher temperatures than those attainable through the ignition at normal atmospheric temperatures of combustible mixtures consisting of pure components in stoichiometric proportions.

I claim:

l. The method of producing hydrazine which comprises directing a heated blast of gases into a reaction zone and forming in the reaction zone a stream of hot gases having a temperature substantially higher than the decomposition temperature of hydrazine, said heated blast of gases being formed by pre-ignition and burning of a combustible mixture of gases at a point adjacent said reaction zone, directing a separate stream of ammonia at a high velocity into contact with the stream of hot gases of combustion within the reaction zone and forming therein a high-temperature gaseous reaction product comprising: (l) hydrazine resulting from transformation of a portion of the ammonia; (2) unaltered ammonia, and 3) products of combustion resulting from pre-ignition and burning of the combustible mixture of gases, removing the high-temperature gaseous reaction product from the hot reaction zone to a cooling zone and cooling said product to a temperature at which hydrazine contained therein is stable, and separating hydrazine from other substances associated therewith in the cooled product, ammonia being introduced into the hot reaction zone; (1) at a rate such as to provide a time of contact of the ammonia with the stream of hot gases of combustion substantially shorter than one one-hundredth (1/100) of a second; (2) at a temperature substantially below the temperature of said heated blast of gases; and (3) in an amount in excess of that required for reaction, such as to aid materially in cooling the gaseous reaction product to la temperature at which hydrazine contained therein is relatively stable.

2. The method of producing hydrazine which comprises directing a heated blast of gases into a reaction zone and forming in the reaction zone a stream of hot gases having a temperature substantially higher than the decomposition temperature of hydrazine, said heated blast of gases being formed by pre-ignition and burning of a combustible mixture of gases at a point adjacent said reaction zone, directing a separate stream of ammonia at a high velocity into contact With the stream of hot gases of combustion Within the reaction zone and forming therein a high-temperature gaseous reaction product comprising: (l) hydrazine resulting from transformation of a portion of the ammonia; (2) unaltered ammonia; and (3) products of combustion resulting from pre-ignition and burning of the combustible mixture of gases, removing the high-temperature gaseous reaction product from the hot reaction zone to a cooling zone and cooling said product to a temperature at which hydrazine contained therein is stable, and separating hydrazine from other substances associated therewith in the cooled product, ammonia being introduced into the hot reaction zone; (1) at a rate such as to provide a time of contact of the ammonia with the stream of hot gases of combustion substantially shorter than one one-hundredth (1/ 100) of a second; (2) at a temperature substantially below the temperature of said heated blast of gases; and (3) in an amount in excess of that required for reaction, such as to aid materially in effecting removal of the gaseous reaction product from the hot reaction zone and in rapidly cooling the gaseous reaction product to a temperature at which hydrazine contained therein is relatively stable.

3. The method of producing hydrazine which comprises directing a heated blast of gases into a reaction zone and forming in the reaction zone a stream of hot gases having a temperature substantially higher than the 5 decomposition temperature of hydrazine, said heated blast of gases being formed by pre-ignition and burning of a combustible mixture of gases including methane at a point adjacent said reaction zone, directing a separate stream of ammonia at a high velocity into contact with the stream of hot gases of combustion in the reaction zone and 'forming therein a high-temperature gaseous reaction product comprising: (l) hydrazine resulting from transformation of a portion of the ammonia; (2) unaltered ammonia; and 3) products of combustion resulting from pre-ignition and burning of the combustible mixture of gases including methane, removing the high-temperature gaseous reaction product from the hot reaction zone to a. cooling zone and cooling said product to a temperature at which hydrazine contained therein is stable, and separating hydrazine from other substances associated in the cooled product, ammonia being introduced into the hot reaction zone; (l) at a rate such as to provide a time of contact of the amomnia with the stream of hot gases of combustion substantially shorter than one onehundredth (1/ 100) of a second; (2) at a temperature substantially below the decomposition temperature of hydrazine; and (3) in an amount in excess of that required for reaction, such as to aid materially in cooling the gaseous reaction product to a temperature at which hydrazine contained therein is relatively stable.

4. The method of producing hydnazine which comprises directing a heated blast of gases into a reaction zone and forming in the reaction zone a stream of hot gases having a temperature substantially higher than the decomposition temperature of hydrazine, said heated blast of gases being formed by pre-ignition and burning of a combustible mixture of gases including methane within a combustion chamber located adjacent said reaction zone and having the hot products of combustion produced therein directed into said reaction zone, directing a separate stream of ammonia at a high velocity into contact with the stream of hot gases of combustion within the reaction zone and forming therein a high-temperature gaseous reaction product comprising: (l) hydrazine resulting from transformation of a portion of the ammonia; (2) unaltered ammonia; and (3) products of combustion resulting from pre-ignition and burning of the combustible mixture of gases including methane, removing the high-temperature gaseous reaction product from the hot reaction zone to a cooling zone and cooling said product to a temperature at which. hydrazine contained therein is stable, and separating hydrazine from other substances associated therewith in the cooled product, ammonia being introduced into the hot reaction zone, (l) at a rate such as to provide a time of contact of the ammonia with the hot stream of gases of combustion substantially shorter than one one-hundredth (l/100) of a second, (2) at a temperature substantially below the decomposition temperature of hydrazine, and (3) in an amount in excess of that required for reaction, such as to aid materially in rapidly cooling the gaseous reaction product to a temperature at which hydrazine contained therein is relatively stable.

References Cited in the tile of this patent UNITED STATES PATENTS McCallum Mar. 2, 1937 McKinnis May 13, 1952 OTHER REFERENCES (A. P. (3.), published 

1. THE METHOD OF PRODUCING HYDRAZINE WHICH COMPRISES DIRECTING A HEATED BLAST OF GASES INTO A REACTION ZONE AND FORMING IN THE REACTION ZONE A STREAM OF HOT GASES HAVING A TEMPERATURE SUBSTANTIALLY HIGHER THAN THE DECOMPOSITION TEMPERATURE OF HYDRAZINE, SAID HEATED BLAST OF GASES BEING FORMED BY PRE-IGNITION AND BURNING OF A COMBUSTIBLE MIXTURE OF GASES AT A POINT ADJACENT SAID REACTION ZONE, DIRECTING A SEPERATE STREAM OF AMMONIA AT A HIGH VELOCITY INTO CONTACT WITH THE STREAM OF HOT GASES OF COMBUSTION WITHIN THE REACTION ZONE AND FORMING THEREIN A HIGH-TEMPERATURE GASEOUS REACTION PRODUCT COMPORISING: (1) HYDRAZINE RESULTING FROM TRANSFORMATION OF A PORTION OF THE AMMONIA; (2) UNALTERED AMMONIA, AND (3) PRODUCTS OF COMBUSTION RESULTING FROM PRE-IGNITION AND BURNING OF THE COMBUSTIBLE MIXTURE OF GASES, REMOVING THE HIGH-TEMPERATURE GASEOUS REACTION PRODUCT FROM THE HOT REACTION ZONE TO A COOLING ZONE AND 